The chemiluminescence (CL) mechanism of oxidophenyl-substituted 1,2-dioxetane was investigated by performing TD-DFT calculations on biradicals of three model compounds. We propose a novel mechanism of CL in which excitation of a dissociative intermediate by infrared radiation (IRE) of the surrounding solvent is considered. The excitation energies and oscillator strengths (f-values) were estimated for intermediates along the reaction coordinate (Rx). The difference in efficiencies of CL between syn- and anti-isomers of m-oxidophenyl-dioxetane is explained using the difference in potential curves of the singlet excited states (S) and the IRE mechanism. At the point where the biradical of the anti-isomer decomposes into two fragments, the interaction between the S and triplet (T) states is induced by a significant back electron transfer (BET) from the dioxetane group to the oxido-phenyl group and the S(1) excited state is stabilized and CL efficiency is enhanced. In the syn-isomer, the barrier in the S(1) potential curve to reach the final CL state is higher than for the anti-isomer, which reduces the efficiency. The poor CL yield for the p-isomer is ascribed to a much higher barrier in the potential curve of the S(1) state.